CA1213687A - Polyester block copolymer composition - Google Patents
Polyester block copolymer compositionInfo
- Publication number
- CA1213687A CA1213687A CA000428812A CA428812A CA1213687A CA 1213687 A CA1213687 A CA 1213687A CA 000428812 A CA000428812 A CA 000428812A CA 428812 A CA428812 A CA 428812A CA 1213687 A CA1213687 A CA 1213687A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- block copolymer
- polyester
- epoxy compound
- terephthalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
Abstract
Abstract:
The invention provides an improved polyester block co-polymer composition having a rubber-like elasticity, and in particular having good moldability, impact resistance, heat resistance and water resistance. The composition comprises a polyester block copolymer produced from a crystalline aro-matic polyester and a lactone in melt-admixture with a poly-tetramethylene terephthalate and optionally further with at least one epoxy compound.
The invention provides an improved polyester block co-polymer composition having a rubber-like elasticity, and in particular having good moldability, impact resistance, heat resistance and water resistance. The composition comprises a polyester block copolymer produced from a crystalline aro-matic polyester and a lactone in melt-admixture with a poly-tetramethylene terephthalate and optionally further with at least one epoxy compound.
Description
~Z13687 Improved PoIyester BIock CopoIymer Cbmposition The present invention relates to an improved polyester block copolymer composition having a rubber-like elasticity.
Polyester block copolymers produced by reacting an aro-5 matic polyester and a lactone, so-called polyester elastomers, have recently been noticed as useful materials for various purposes because of their excellent properties such as heat resistance, light resistance, low-temperature characteristics, and the like. It is well known to produce such polyester 10 block copolymers by reacting an aromatic polyester and a lac-tone, for example, by reacting a crystalline aromatic poly-ester and a lactone (cf. Japanese Patent Publication No. 4116/
1973); by reacting a crystalline aromatic polyester and a lactone, followed by reacting the resulting block prepolymer 15 with a polyfunctional acylating agent to extend the chain of the polymer (cf. Japanese Patent Publication No. 4115/1973);
or by polymerizing a lactone in the presence of a crystalline aromatic polyester in solid state (cf. Japanese Patent Publi-cation No. 49037/1977). However, because of their low vis-20 cosities and low heat distortion temperatures, these knownpolymers are restricted in their applications. Por instance, lZ1368~7 when they are used for injection molding, because of their low viscosities, many mold flashes occur, and further, because of their low heat distortion temperatures, the molded products are easily deformed by knockout pins af~er short cooling times.
It is also known to add an inorganic filler, such as talc, to the polyesters as a nucleating agent in order to im-prove the moldability of the polyesters. According to this method, the Vicat softening temperature and crystallization temperature thereof may be improved, but the tensile strength 10 at break is significantly decreased. Besides, the viscosity of the polymers cannot be increaséd by the addition of an inorganic ~iller.
The present inventors have carried out an extensive study of methods for obtaining polyester compositions of improved 15 moldability. As a result, it has been found that a poly-tetramethylene terephthalate is effective for such a purpose.
Polytetramethylene terephthalate has excellent mechanical characteristics such as excellent tenacity, wear resistance, etc. and hence is usually used for various molding products
Polyester block copolymers produced by reacting an aro-5 matic polyester and a lactone, so-called polyester elastomers, have recently been noticed as useful materials for various purposes because of their excellent properties such as heat resistance, light resistance, low-temperature characteristics, and the like. It is well known to produce such polyester 10 block copolymers by reacting an aromatic polyester and a lac-tone, for example, by reacting a crystalline aromatic poly-ester and a lactone (cf. Japanese Patent Publication No. 4116/
1973); by reacting a crystalline aromatic polyester and a lactone, followed by reacting the resulting block prepolymer 15 with a polyfunctional acylating agent to extend the chain of the polymer (cf. Japanese Patent Publication No. 4115/1973);
or by polymerizing a lactone in the presence of a crystalline aromatic polyester in solid state (cf. Japanese Patent Publi-cation No. 49037/1977). However, because of their low vis-20 cosities and low heat distortion temperatures, these knownpolymers are restricted in their applications. Por instance, lZ1368~7 when they are used for injection molding, because of their low viscosities, many mold flashes occur, and further, because of their low heat distortion temperatures, the molded products are easily deformed by knockout pins af~er short cooling times.
It is also known to add an inorganic filler, such as talc, to the polyesters as a nucleating agent in order to im-prove the moldability of the polyesters. According to this method, the Vicat softening temperature and crystallization temperature thereof may be improved, but the tensile strength 10 at break is significantly decreased. Besides, the viscosity of the polymers cannot be increaséd by the addition of an inorganic ~iller.
The present inventors have carried out an extensive study of methods for obtaining polyester compositions of improved 15 moldability. As a result, it has been found that a poly-tetramethylene terephthalate is effective for such a purpose.
Polytetramethylene terephthalate has excellent mechanical characteristics such as excellent tenacity, wear resistance, etc. and hence is usually used for various molding products
2~ as an engineering plastic. However, this resin has drawbacks such as inferior impact resistance and inferior low-temperature characteristics, and the like. In order to eliminate such drawbacks, attempts have been made to incorporate elastic resins therewith SUC]l as various rubbers or polyurethane elas-25 tomers, but it results in a lowering of mechanical character-istics such as tenacity and wear resistance, because of low compatibility and affinity between the resins.
Nevertheless, it has now been found that when a poly-ester block copolymer produced by reacting a crystalline aro-matic polyester and a lactone is mixed with a polytetramethy-lene terel~]ltl~ te, a composition having good moldability, S impact resistance, and other properties can be obtained with-out adversely affecting the desirable mechanical character-istics of the polytetramethylene terephthalate.
Thus, according to the invention there is provided a polyester block copolymer composition which comprises 2 to 95 parts by weight of a polyester block copolymer obtained from a crystalline aromatic polyester and a lactone, and 98 to 5 parts by weight of a polytetramethylene terephthal-ate, and wherein a mono- or more functional epoxy compound is incorporated therein in an amount of 0.2 to 10 ~ by weight based on the total weight of the composition.
An advarltage of the present invention, at least in preferred forms, is that is can provide an improved polyester block copolyrller composition having improved moldability in addition to other desirable properties. Another advantage of the invention, at least in preferred forms, is that it can provide an improvement of polyester block copolyester compo-sitions in various properties such as impact resistance, flex-ibility, moldability, low-temperature characteristics or the like by incorporating a polytetramethylene terephthalate without adversely affecting the mechanical characteristics .~ ~
~1368 of the polytetrame~hylcne terephthalate. A further advantage of thc invcntion, at least in the prcfcrred forms, is that it can provide a polyester block copolymcr composition having improvcd heat rcsistance, water resistance and impact resist-ance. A still further advantage of the invention, at leastin preferred forms, is that it can provide a further improve-ment of additional propertics of a polycster block copolymer composition by incorporating a combination of a polytctra-mcthylene terephthalate and an epoxy compound.
The composition of the present invention has good heat resistance and light resistance and also has a iligh heat distortion temperaturc and a high crystallization temperaturc, and hencc, it has high melt viscosity and wide rangc of hardnesses (i.e. such that any desircd hardness can ~c frccly selected), and it can easily be used not only for injcction molding but also for extrusion molding, which mcans that the composi~ion of the prcsent invcntion is useful for a wider ficld of applications. Moreover, the cornposition of the present invention has superior impact resistance in comparison with a conventional polyester block copolymer.
The polyester block copolymer and the polytetra-methylene terephthalate have good compatibility, and hence, the composition of the present invention can produce good molded products without the occurrence of undesirable ^~: lamellar peeling. The molded products produced from the r~
~.
:lhl3~87 compositions of the present invention are also character-istic in having good surface gloss.
Both the main reslns used in the composition of the present invention are polyester type resins, and have good affinity and compatibility for each other, and hence, the compositions have various improved properties such as im-pact resistance, flexibility, moldability, low-temperature characteristics or the like without adversely affecting the peculiar mechanical characteristics of the polytetra-methylene terephthalate. Moreover, by incorporating an epoxy compound in addition to the polytetramethylene terephthalate into the polyester block copolymer, a polyester elastomer having excellent heat resistance, hydrolysis resistance and impact resistance can be lS obtained.
The crystalline aromatic polyester used in the present invention is a polymer predominantly formed by ester linkages or a combination of ester linkage and èther linkages, which has a main repeating unit of at least one aromatic group and has a terminal hydroxy group. The crystalline aromatic polyester preferably has a melting point of 150C or higher in the case of a high degree ~13~87 of polymerization. For the purpose of utilizing the final composition as a molding material, the crystalline aromatic polyester preferably has a molecular weight of not less than 5,000, more preferably not less than 8,000. For the purpose of utilizin~ the final composition as an adhesive or coating material, the polyester may have a molecular weight of less than 5,000.
Suitable examples of the crystalline aromatic polyester are homopolyesters e.g. polyethylene terephthalate, polytetramethylene terephthalate, poly-l, 4-cyclohexylene-dimethylene terephthalate, polyethylene 2,6-naphthalate;
polyester ethers e.g. polyethylene hydroxybenzoate, poly-p-phenylene bishydroxyethoxyterephthalate; copolyesters or copolyester ethers which comprise mainly tetramethylene terephthalate units or ethylene terephthalate units and other copolymer components e.g. tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units, tetramethylene or ethylene sebacate units, 1,4-cyclohexylenedimethylene terephthalate units, or tetra-methylene or ethylene p-hydroxybenzoate units, or the like.
The copolymers preferably contain 60 molar % or more of tetramethylene terephthalate units or ethylene terephtha-late units.
The lactone is most preferably ~-caprolactone, but other la~tones e.g. enantholactone or caprilolactone may also be used. Two or more lactones may be used together.
The above crystalline aromatic copolyester and lactone can be copolymerized in an appropriate ratio, which depends ~36~37 on the intended application of the final composition. Gene-rally, as the amount of the aromatic polyester is increased, the polymer becomes harder and shows improved mechanical characteristics such as strength, and on the other hand, as 5 the amount of the lactone is increased, the polymer becomes softer and shows improved properties at low temperatures.
Accordingly, it is preferable to use the aromatic polyester/
lactone in the ratio of 9S/5 to Sl95 by weight, more prefer-ably ~0/20 to 30/70 by weight.
The reaction of the crystalline polyester and the lactone for producing the desired polyester type block copolymer may be carried out in the presence or absence of a catalyst.
The polytetramethylene terephthalate used in the present invention may be a homopolyester or may be a copolyester com-15 prising mainly tetramethylene terephthalate units and units ofother copolymerizable components e.g. ethylene terephthalate units, tetramethylene isophthalate units, tetramethylene adipate units~ tetramethylene sebacate units, l,~-cyclohexylene dimethylene terephthalate units, etc. The copolyesters com-20 prise 80 molar % or more of the tetramethylene terephthalateullit.
The composition of the present invention comprises 2 to 95 parts by weight of the polyester block copolymer and 98 to 5 parts by weight of the polytetramethylene terephthalate.
25 When the amount of the polyester block copolymer is less than 2 parts by weight and the amount of the polytetramethylene terephthalate is above 98 parts by weight, the product obtained , ~ ~ .
~Z~368~
from the composition shows significantly decreased Izod impact strength and does not show any improvement in the impact re-sistance of the polytetramethylene terephthalate. On the other hand, when the amount of the polyester block copolymer 5 is above 95 parts by weight and the amount of the polytetra-methylene terephthalate is less than 5 parts by weight, the composition shows a low crystallization temperature and does not show any improvement in moldability and also in Vicat soften~g point.
The compositions comprising 25 to 95 parts by weight of a polyester block copolymer, said copolymer having a lactone con~ent of 5 to 95 ~ by weight, preferably 20 to 70 ~ by weight, and 75 to 5 parts by weight of a polytetramethylene terephthalate have particularly good moldability and impact 15 resistance. The compositions comprising 2 to 24 parts by weight of a polyester block copolymer, said copolymer having a lactone content of 20 to 70 ~ by weight, preferably 25 to 50 % by weight, and 98 to 76 parts by weight of a polytetra-methylene terephthalate have greatly improved properties e.g.
20 good impact resistance, flexibility, moldability, low-temp-erature characteristics, etc. without adversely affecting the desirable mechanical characteristics of the polytetra-methylene terephthalate.
The epoxy compounds that may be used in the present in-25 vention are not limited in any way provided they have at least one epoxy group within the molecule. Suitable epoxy compounds are those of the following formulae (I), ~II) and . , :` ~
i2136~37 g (III):
Rl----(R20)m--CH2--CH CH2 (I) O
CH~--CH--CH2--O--R3--O--cH --CH CH (II) O . O
(CH~--CH-C~I2~0-) 3_~4 (III) O
wherein Rlis a hydrocarbon group having 1 to 10 carbon atoms, 5 R2 is an al~ylene group having 1 to 4 carbon atoms, R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or -(R20)m-R2-, R4 is a trivalent hydrocarbon group having 3 to 20 carbon atoms, and m is 0 or an integer of 1 to 20.
Suitable examples are methyl glycidyl ether, phenyl gly-10 cidyl ether, ethylene glycol diglycidyl ether, diethyleneglycol diglycidyl ether, polyethlene glycol monophenyl mono-glycidyl ether, glycerine triglycidyl ether, or the like.
The above epoxy compounds preferably have an epoxy value of 0.9 to 14 equivalent~kg.
lS Di-or more functional epoxy compounds, e.g. di- or tri-functional epoxy compounds of the formulae (II) and (III), are preferably used, and optionally, a monoepoxy compound is used therewith.
The required amount of the epoxy compound depends on the 20 amount of the terminal groups of the polyester block copoly-mer and polytetramethylene terephthalate, but is usually in the range of 0.2 to 10 ~ by weight, preferably 0.4 to 4 ~ by wcight, based on the weight of the polycster block copolymer , --~213687 and polytetramethylene terephthalate. When the amount is less than 0.2 ~ by weight, the effect of the epoxy compound on the improYement of heat aging resistance and hydrolysis resistance is reduced, but on the other hand, when the amount is above 5 10 ~ by weight, the molded product obtained from the final composition has a disadvantageously crude surface due to the unreacted epoxy compound. It is particularly preferable to use a mono-functional epoxy compound in an amount of 0.1 to 5 ~ by weight and a di- or more functional epoxy compound in 10 an amount of 0.1 to 9.9 % by weight.
When the epoxy compound is melt-admixed with the poly-ester block copolymer and polytetramethylene terephthalate, a reaction of the polyester block copolymer and polytetra-methylene terephthalate with the epoxy compound may take place 15 in the absence of a catalyst, but is remarkably promoted by using a catalyst. The catalyst may be any conventional cata-lyst usually used in the reaction of epoxy compounds, for ex mple, amines, phosphorus compounds, and a salt of a mono-and/or di-carboxylic acid having 10 or more carbon atoms with a 20 metal of the group I-a or II-a in Period Table. Particularly suitable examples of the catalyst are trivalent phosphorus compounds e.g. tributylphosphine and triphenylphosphine.
These catalysts may be used as a combination of two or more thereof. The above epoxy compounds and catalysts may be added 25 to the reaction system either all at the same time or in por-tions over a period of time.
The improved polyester block copolymer composition of .~ -,,,~,.
lZ136~3~
the present invention can be prepared by conventional methods, for example, by mixing polyes~er block copolymer chips with polytetramethylene terephthalate, an epoxy compound, catalyst and other additives and uniformly melt-admixing them with 5 heating. The melt-admixing is preferably carried out at a temperature of 3C higher than the melting point of the cry-stalline elastomer to 280C for about 30 seconds to 120 minutes.
The mixing period may vary according to the kinds of mixing methods and temperature. During the melt-mixing, the various 10 additives e.g. pigments, stabilizers and the like may be added to the composition without adversely affecting the improvement of hydrolysis resistance, heat;aging resistance, and impact resistance.
The polyester block copolymer composition of the present 15 invention has good moldability, impact resistance, heat re-sistance and water resistance, and hence, can be used for various purposes, such as injection moldings, blow moldings and extrusion moldings useful as parts of various machines and other molding products, such as name plates, automobile 20 parts, switches, holders, hooks, packings, resin springs, fastener, various coverings, gears, belts, rolls, bottles, tubes, hoses, films, sheets, vibration insulators or dampers, coatings (e.g. wire coatings), and the like.
The present invention is illustrated by the following 25 Examples but should not be construed to be limited thereto.
In the Examples, the various properties were measured by the following methods:
(1) Reduced specific viscosity This was measured under the following conditions:
Solvent: Phenol~tetrachloroethane (6/4 by weight) Concentration: 50 mg~25 ml Temperature: 30C
(2) Melt viscosity This was measured at 240C under a load of 50 kg/cm2 with a Koka flow tester.
Nevertheless, it has now been found that when a poly-ester block copolymer produced by reacting a crystalline aro-matic polyester and a lactone is mixed with a polytetramethy-lene terel~]ltl~ te, a composition having good moldability, S impact resistance, and other properties can be obtained with-out adversely affecting the desirable mechanical character-istics of the polytetramethylene terephthalate.
Thus, according to the invention there is provided a polyester block copolymer composition which comprises 2 to 95 parts by weight of a polyester block copolymer obtained from a crystalline aromatic polyester and a lactone, and 98 to 5 parts by weight of a polytetramethylene terephthal-ate, and wherein a mono- or more functional epoxy compound is incorporated therein in an amount of 0.2 to 10 ~ by weight based on the total weight of the composition.
An advarltage of the present invention, at least in preferred forms, is that is can provide an improved polyester block copolyrller composition having improved moldability in addition to other desirable properties. Another advantage of the invention, at least in preferred forms, is that it can provide an improvement of polyester block copolyester compo-sitions in various properties such as impact resistance, flex-ibility, moldability, low-temperature characteristics or the like by incorporating a polytetramethylene terephthalate without adversely affecting the mechanical characteristics .~ ~
~1368 of the polytetrame~hylcne terephthalate. A further advantage of thc invcntion, at least in the prcfcrred forms, is that it can provide a polyester block copolymcr composition having improvcd heat rcsistance, water resistance and impact resist-ance. A still further advantage of the invention, at leastin preferred forms, is that it can provide a further improve-ment of additional propertics of a polycster block copolymer composition by incorporating a combination of a polytctra-mcthylene terephthalate and an epoxy compound.
The composition of the present invention has good heat resistance and light resistance and also has a iligh heat distortion temperaturc and a high crystallization temperaturc, and hencc, it has high melt viscosity and wide rangc of hardnesses (i.e. such that any desircd hardness can ~c frccly selected), and it can easily be used not only for injcction molding but also for extrusion molding, which mcans that the composi~ion of the prcsent invcntion is useful for a wider ficld of applications. Moreover, the cornposition of the present invention has superior impact resistance in comparison with a conventional polyester block copolymer.
The polyester block copolymer and the polytetra-methylene terephthalate have good compatibility, and hence, the composition of the present invention can produce good molded products without the occurrence of undesirable ^~: lamellar peeling. The molded products produced from the r~
~.
:lhl3~87 compositions of the present invention are also character-istic in having good surface gloss.
Both the main reslns used in the composition of the present invention are polyester type resins, and have good affinity and compatibility for each other, and hence, the compositions have various improved properties such as im-pact resistance, flexibility, moldability, low-temperature characteristics or the like without adversely affecting the peculiar mechanical characteristics of the polytetra-methylene terephthalate. Moreover, by incorporating an epoxy compound in addition to the polytetramethylene terephthalate into the polyester block copolymer, a polyester elastomer having excellent heat resistance, hydrolysis resistance and impact resistance can be lS obtained.
The crystalline aromatic polyester used in the present invention is a polymer predominantly formed by ester linkages or a combination of ester linkage and èther linkages, which has a main repeating unit of at least one aromatic group and has a terminal hydroxy group. The crystalline aromatic polyester preferably has a melting point of 150C or higher in the case of a high degree ~13~87 of polymerization. For the purpose of utilizing the final composition as a molding material, the crystalline aromatic polyester preferably has a molecular weight of not less than 5,000, more preferably not less than 8,000. For the purpose of utilizin~ the final composition as an adhesive or coating material, the polyester may have a molecular weight of less than 5,000.
Suitable examples of the crystalline aromatic polyester are homopolyesters e.g. polyethylene terephthalate, polytetramethylene terephthalate, poly-l, 4-cyclohexylene-dimethylene terephthalate, polyethylene 2,6-naphthalate;
polyester ethers e.g. polyethylene hydroxybenzoate, poly-p-phenylene bishydroxyethoxyterephthalate; copolyesters or copolyester ethers which comprise mainly tetramethylene terephthalate units or ethylene terephthalate units and other copolymer components e.g. tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units, tetramethylene or ethylene sebacate units, 1,4-cyclohexylenedimethylene terephthalate units, or tetra-methylene or ethylene p-hydroxybenzoate units, or the like.
The copolymers preferably contain 60 molar % or more of tetramethylene terephthalate units or ethylene terephtha-late units.
The lactone is most preferably ~-caprolactone, but other la~tones e.g. enantholactone or caprilolactone may also be used. Two or more lactones may be used together.
The above crystalline aromatic copolyester and lactone can be copolymerized in an appropriate ratio, which depends ~36~37 on the intended application of the final composition. Gene-rally, as the amount of the aromatic polyester is increased, the polymer becomes harder and shows improved mechanical characteristics such as strength, and on the other hand, as 5 the amount of the lactone is increased, the polymer becomes softer and shows improved properties at low temperatures.
Accordingly, it is preferable to use the aromatic polyester/
lactone in the ratio of 9S/5 to Sl95 by weight, more prefer-ably ~0/20 to 30/70 by weight.
The reaction of the crystalline polyester and the lactone for producing the desired polyester type block copolymer may be carried out in the presence or absence of a catalyst.
The polytetramethylene terephthalate used in the present invention may be a homopolyester or may be a copolyester com-15 prising mainly tetramethylene terephthalate units and units ofother copolymerizable components e.g. ethylene terephthalate units, tetramethylene isophthalate units, tetramethylene adipate units~ tetramethylene sebacate units, l,~-cyclohexylene dimethylene terephthalate units, etc. The copolyesters com-20 prise 80 molar % or more of the tetramethylene terephthalateullit.
The composition of the present invention comprises 2 to 95 parts by weight of the polyester block copolymer and 98 to 5 parts by weight of the polytetramethylene terephthalate.
25 When the amount of the polyester block copolymer is less than 2 parts by weight and the amount of the polytetramethylene terephthalate is above 98 parts by weight, the product obtained , ~ ~ .
~Z~368~
from the composition shows significantly decreased Izod impact strength and does not show any improvement in the impact re-sistance of the polytetramethylene terephthalate. On the other hand, when the amount of the polyester block copolymer 5 is above 95 parts by weight and the amount of the polytetra-methylene terephthalate is less than 5 parts by weight, the composition shows a low crystallization temperature and does not show any improvement in moldability and also in Vicat soften~g point.
The compositions comprising 25 to 95 parts by weight of a polyester block copolymer, said copolymer having a lactone con~ent of 5 to 95 ~ by weight, preferably 20 to 70 ~ by weight, and 75 to 5 parts by weight of a polytetramethylene terephthalate have particularly good moldability and impact 15 resistance. The compositions comprising 2 to 24 parts by weight of a polyester block copolymer, said copolymer having a lactone content of 20 to 70 ~ by weight, preferably 25 to 50 % by weight, and 98 to 76 parts by weight of a polytetra-methylene terephthalate have greatly improved properties e.g.
20 good impact resistance, flexibility, moldability, low-temp-erature characteristics, etc. without adversely affecting the desirable mechanical characteristics of the polytetra-methylene terephthalate.
The epoxy compounds that may be used in the present in-25 vention are not limited in any way provided they have at least one epoxy group within the molecule. Suitable epoxy compounds are those of the following formulae (I), ~II) and . , :` ~
i2136~37 g (III):
Rl----(R20)m--CH2--CH CH2 (I) O
CH~--CH--CH2--O--R3--O--cH --CH CH (II) O . O
(CH~--CH-C~I2~0-) 3_~4 (III) O
wherein Rlis a hydrocarbon group having 1 to 10 carbon atoms, 5 R2 is an al~ylene group having 1 to 4 carbon atoms, R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or -(R20)m-R2-, R4 is a trivalent hydrocarbon group having 3 to 20 carbon atoms, and m is 0 or an integer of 1 to 20.
Suitable examples are methyl glycidyl ether, phenyl gly-10 cidyl ether, ethylene glycol diglycidyl ether, diethyleneglycol diglycidyl ether, polyethlene glycol monophenyl mono-glycidyl ether, glycerine triglycidyl ether, or the like.
The above epoxy compounds preferably have an epoxy value of 0.9 to 14 equivalent~kg.
lS Di-or more functional epoxy compounds, e.g. di- or tri-functional epoxy compounds of the formulae (II) and (III), are preferably used, and optionally, a monoepoxy compound is used therewith.
The required amount of the epoxy compound depends on the 20 amount of the terminal groups of the polyester block copoly-mer and polytetramethylene terephthalate, but is usually in the range of 0.2 to 10 ~ by weight, preferably 0.4 to 4 ~ by wcight, based on the weight of the polycster block copolymer , --~213687 and polytetramethylene terephthalate. When the amount is less than 0.2 ~ by weight, the effect of the epoxy compound on the improYement of heat aging resistance and hydrolysis resistance is reduced, but on the other hand, when the amount is above 5 10 ~ by weight, the molded product obtained from the final composition has a disadvantageously crude surface due to the unreacted epoxy compound. It is particularly preferable to use a mono-functional epoxy compound in an amount of 0.1 to 5 ~ by weight and a di- or more functional epoxy compound in 10 an amount of 0.1 to 9.9 % by weight.
When the epoxy compound is melt-admixed with the poly-ester block copolymer and polytetramethylene terephthalate, a reaction of the polyester block copolymer and polytetra-methylene terephthalate with the epoxy compound may take place 15 in the absence of a catalyst, but is remarkably promoted by using a catalyst. The catalyst may be any conventional cata-lyst usually used in the reaction of epoxy compounds, for ex mple, amines, phosphorus compounds, and a salt of a mono-and/or di-carboxylic acid having 10 or more carbon atoms with a 20 metal of the group I-a or II-a in Period Table. Particularly suitable examples of the catalyst are trivalent phosphorus compounds e.g. tributylphosphine and triphenylphosphine.
These catalysts may be used as a combination of two or more thereof. The above epoxy compounds and catalysts may be added 25 to the reaction system either all at the same time or in por-tions over a period of time.
The improved polyester block copolymer composition of .~ -,,,~,.
lZ136~3~
the present invention can be prepared by conventional methods, for example, by mixing polyes~er block copolymer chips with polytetramethylene terephthalate, an epoxy compound, catalyst and other additives and uniformly melt-admixing them with 5 heating. The melt-admixing is preferably carried out at a temperature of 3C higher than the melting point of the cry-stalline elastomer to 280C for about 30 seconds to 120 minutes.
The mixing period may vary according to the kinds of mixing methods and temperature. During the melt-mixing, the various 10 additives e.g. pigments, stabilizers and the like may be added to the composition without adversely affecting the improvement of hydrolysis resistance, heat;aging resistance, and impact resistance.
The polyester block copolymer composition of the present 15 invention has good moldability, impact resistance, heat re-sistance and water resistance, and hence, can be used for various purposes, such as injection moldings, blow moldings and extrusion moldings useful as parts of various machines and other molding products, such as name plates, automobile 20 parts, switches, holders, hooks, packings, resin springs, fastener, various coverings, gears, belts, rolls, bottles, tubes, hoses, films, sheets, vibration insulators or dampers, coatings (e.g. wire coatings), and the like.
The present invention is illustrated by the following 25 Examples but should not be construed to be limited thereto.
In the Examples, the various properties were measured by the following methods:
(1) Reduced specific viscosity This was measured under the following conditions:
Solvent: Phenol~tetrachloroethane (6/4 by weight) Concentration: 50 mg~25 ml Temperature: 30C
(2) Melt viscosity This was measured at 240C under a load of 50 kg/cm2 with a Koka flow tester.
(3) Melting and crystalliza~ion temperature The melting temperature is shown by an endotherm peak when a sample was heated with raising the temperature at a rate of 20 C/minute with a differcntial scanning calorimeter (manufactured by Perkin-Elemmer Co.,), and the crystallization temperature is shown by an exotherm peak when the sample was 15 cooled from the temperature 20C higher than the melting point at a cooling rate of -20C/minutes.
(4) Thermal deformation temperature This was measured by the method as defined in Japan Industrial Standards (JIS) K7207.
(5) Vicat softening point This was measured by the method as defined in Japanese Industrial Standards (JIS) K7206.
(6) Tensile strength, tensile elongation and elastic modulus in tension The starting chips were heat-pressed to form a flat plate (thickness: 2mm), which was punched to form a Dumbbell-shaped test piece. The test piece was drawn at a rate of lZ~368~
50 mm/minute, and the weight (kg) of the load was measured at the break of the test p;ece. The tensile strength (kg/cm2) was shown by a value obtained by dividing the load (kg) at break by the initial sectional area ~cm2) of the test piece. The tensile elongation (%) was shown by the ratio of elongation of the test piece at break to the length of the starting test piece. Besides, the elastic modulus in tension was calculated from a curve of the stress-elongation at this time.
50 mm/minute, and the weight (kg) of the load was measured at the break of the test p;ece. The tensile strength (kg/cm2) was shown by a value obtained by dividing the load (kg) at break by the initial sectional area ~cm2) of the test piece. The tensile elongation (%) was shown by the ratio of elongation of the test piece at break to the length of the starting test piece. Besides, the elastic modulus in tension was calculated from a curve of the stress-elongation at this time.
(7) Izod impact strength (with notch) This was measured by the method as defined in ASTM
D256.
1~
12~36~
Preparation 1 Polytetramethylene terephthalate (70 kg) and ~-caprolactone (30 kg) were charged into a reactor. After purging the reactor with nitrogen gas, the mixture was melt-reacted with stirring at 230C for 2 hours. The unreacted -caprolactone was removed in vacuum. The polyester elastomer (A) thus obtained had a reduced specific viscosity of 1.163, and further had a tensile strength at break of 371 kg/cm2 and a tensile elongation at break of 708 10 ~-Preparation 2 Polytetramethylene terephthalate (50 kg) and ~-caprolactone (50 kg1 were charged into a reactor. After purging the reactor with nitrogen gas, the mixture was melt-reacted with stirring at 230C for 2 hours. The unreacted -caProlactone was removed in vacuum. The polyester elastomer (B) thus obtained had a reduced specific viscosity of 1.35, and further had a tensile strength at break of 235 kg/cm and a tensile elongation at break of 803 ~.
Example 1 The polyester type block copolymer chips (8 kg) prepared in Preparation 1 and polytetramethylene terephthalate (~sp/c = 1.13) (2 kg) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was extruded with a biaxial extruder 140 mm~). After cooling with water, the ,.
~ ~..
1i213687 extruded product was cut to give chips~ The resulting chips had a reduced specific viscosity of 1.160, a tensile strength at break of 368 kg/cm and a tensile elongation at break of 625 %.
Example 2 The polyester type block copolymer (5 kg) prepared in Preparation 1 and polytetramethylene terephthalate (~sp/c = 1.13) ~5 kg) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes and treated with a biaxial extruder in the same manner as described in Example 1. The chips thus obtained had a reduced specific viscosity of 1.162, a tensile strength at break of 376 kg/cm2 and a tensile elongation at break of 433 %.
Reference Example 1 The polyester type block copolymer (8 kg) prepared in Preparation 1 and talc (2 kg) were charged into a drum tumbler, and the mixture was stirred for 30 minutes and treated in the same manner as described in Example 2. The chips thus obtained had a reduced specific viscosity of 1.161, a tensile strength at break of 178 kg/cm2 and a tensile elongation at break of 495 %.
Example 3 The chips prepared in Examples 1 and 2 and Reference Example 1 were dried at 100C in vacuum and then were formed into a sheet (thickness: 2 mm) with hot-pressing. The hardness and tensile strength at break .,... ~ ~
.
I
~13~87 and tensile elongation at break of the sheet thus obtained were measured. The results are shown in Table 1.
Table 1 ~ . .. .. _ ..... _ .~
Ex. No. Tensile Tensile Elastic Hardness Hardness strength elongation modulus (JIS A) (Shore D) at bre~k at break at ten~ion (kg/cm ) (%) (kg/cm ) . . _ _ Preparn. 1 371708 2311 95 56 Ex. 1 368 6253519 96 65 Ex. 2 376 4334861 97 72 Ref.Ex.l 178 4955660 __ _ _ 67 Example 4 The chips prepared in Preparation 1, Examples 1 and 2, and Reference Example 1 were molded with an injection molding machine to prepare a test piece for measuring the thermal deformation temperature. The thermal deformation temperature as well as melting temperature, crystallization temperature and viscosity of the test pieces were measured in the methods as mentioned hereinbefore. The results are shown in Table 2.
6~7 Table 2 Ex. No. Thermal Vicat DSC DSC Melt deforma- soften- melt- crystalli~ viscosity tion temp. ing temp. ing poin zation temp. at 240C
(C) (C3 (~) (C) (pois) reparn. 1 102.5 187.5 208.5 159.0 1300 l x. 1 115.5 194.0 207.5 163.0 3050 5x. 2 143.8 204.5 211.5 178.5 8500 ~ef.Ex.l 103.6 205.4 212.0 180 1270 Besides, the molded products obtained from the chips prepared in Example 1 and Example 2 showed an Izod impact strength (with notch) of 16.7 kg.cm/cm and 8.7 kg.cm/cm, respectively. The molded product obtained from the polytetramethylene terephthalate shows an Izod impact strength (with notch) of 3.4 kg.cm/cm.
Example 5 The polyester type block copolymer chips prepared in Preparation 1 or 2 and polytetramethylene terephthalate (7 sp/c = 1.13) were charged into a drum tumbler, and the mixture was stirred at room tempexature for 30 minutes.
The resulting mixture was extruded with a biaxial extruder (40 mm~). After cooling with water, the extruded product was cut to give chips. The reducing specific viscosity, tensile strength at break and tensile elongation at break of the resulting chips are shown in Table 3.
The chips obtained above were dried at 100C in vacuum and then were formed into a sheet (thickness: 2 mm) with hot-pressing, and the elastic modulus in tension lZ13687 thereof was measured. The results are shown in Table 3.
Moreover, the chips were molded with an injection molding machine to prepare a test piece for measuring Izod impact strength, and the Izod impact strength was measured in the method as described hereinbefore. The results are also shown in Table 3.
, ., 12~3687 o o~ ~ I` o o oo rm ~ ~ a~
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.. . ._. _ . _ 12~ 7 Example 6 The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate (~
sp/c = 1.13) (5 kg), phenyl glycidyl ether (200 g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was extruded with a biaxial extruder (40 mm~)at 230C. After cooling with water, the extruded product was cut to give chips. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example 7 The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate (~sp/c = 1.13) (5 kg), phenyl glycidyl ether (100 g), diethyleneglycol diglycidyl ether (70 g) and triphenylphos-phine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example B
The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate ( ~sp/c = 1.13) (5 kg), diethyleneglycol diglycidyl ether (140 't'~
g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example 9 The polyester type block copolymer chips prepared in Preparation 1 (8 kg), polytetramethylene terephthalate (~
sp/c = 1.13) (2 kg), phenyl glycidyl ether (100 g), diethyleneglycol diglycidyl ether (70 g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, t~nsile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Table 4 . ~ ..
Ex. No ~sp/c Tensile Tensile Elastic Izod strength elongation modulus impact at bre~k at break at ten~ion strength , (kg/cm ) (%) (kg/cm )(kg cm/cm) 6 1.161 375 425 4670 8.8 7 1.314 467 415 4130 13.4
D256.
1~
12~36~
Preparation 1 Polytetramethylene terephthalate (70 kg) and ~-caprolactone (30 kg) were charged into a reactor. After purging the reactor with nitrogen gas, the mixture was melt-reacted with stirring at 230C for 2 hours. The unreacted -caprolactone was removed in vacuum. The polyester elastomer (A) thus obtained had a reduced specific viscosity of 1.163, and further had a tensile strength at break of 371 kg/cm2 and a tensile elongation at break of 708 10 ~-Preparation 2 Polytetramethylene terephthalate (50 kg) and ~-caprolactone (50 kg1 were charged into a reactor. After purging the reactor with nitrogen gas, the mixture was melt-reacted with stirring at 230C for 2 hours. The unreacted -caProlactone was removed in vacuum. The polyester elastomer (B) thus obtained had a reduced specific viscosity of 1.35, and further had a tensile strength at break of 235 kg/cm and a tensile elongation at break of 803 ~.
Example 1 The polyester type block copolymer chips (8 kg) prepared in Preparation 1 and polytetramethylene terephthalate (~sp/c = 1.13) (2 kg) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was extruded with a biaxial extruder 140 mm~). After cooling with water, the ,.
~ ~..
1i213687 extruded product was cut to give chips~ The resulting chips had a reduced specific viscosity of 1.160, a tensile strength at break of 368 kg/cm and a tensile elongation at break of 625 %.
Example 2 The polyester type block copolymer (5 kg) prepared in Preparation 1 and polytetramethylene terephthalate (~sp/c = 1.13) ~5 kg) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes and treated with a biaxial extruder in the same manner as described in Example 1. The chips thus obtained had a reduced specific viscosity of 1.162, a tensile strength at break of 376 kg/cm2 and a tensile elongation at break of 433 %.
Reference Example 1 The polyester type block copolymer (8 kg) prepared in Preparation 1 and talc (2 kg) were charged into a drum tumbler, and the mixture was stirred for 30 minutes and treated in the same manner as described in Example 2. The chips thus obtained had a reduced specific viscosity of 1.161, a tensile strength at break of 178 kg/cm2 and a tensile elongation at break of 495 %.
Example 3 The chips prepared in Examples 1 and 2 and Reference Example 1 were dried at 100C in vacuum and then were formed into a sheet (thickness: 2 mm) with hot-pressing. The hardness and tensile strength at break .,... ~ ~
.
I
~13~87 and tensile elongation at break of the sheet thus obtained were measured. The results are shown in Table 1.
Table 1 ~ . .. .. _ ..... _ .~
Ex. No. Tensile Tensile Elastic Hardness Hardness strength elongation modulus (JIS A) (Shore D) at bre~k at break at ten~ion (kg/cm ) (%) (kg/cm ) . . _ _ Preparn. 1 371708 2311 95 56 Ex. 1 368 6253519 96 65 Ex. 2 376 4334861 97 72 Ref.Ex.l 178 4955660 __ _ _ 67 Example 4 The chips prepared in Preparation 1, Examples 1 and 2, and Reference Example 1 were molded with an injection molding machine to prepare a test piece for measuring the thermal deformation temperature. The thermal deformation temperature as well as melting temperature, crystallization temperature and viscosity of the test pieces were measured in the methods as mentioned hereinbefore. The results are shown in Table 2.
6~7 Table 2 Ex. No. Thermal Vicat DSC DSC Melt deforma- soften- melt- crystalli~ viscosity tion temp. ing temp. ing poin zation temp. at 240C
(C) (C3 (~) (C) (pois) reparn. 1 102.5 187.5 208.5 159.0 1300 l x. 1 115.5 194.0 207.5 163.0 3050 5x. 2 143.8 204.5 211.5 178.5 8500 ~ef.Ex.l 103.6 205.4 212.0 180 1270 Besides, the molded products obtained from the chips prepared in Example 1 and Example 2 showed an Izod impact strength (with notch) of 16.7 kg.cm/cm and 8.7 kg.cm/cm, respectively. The molded product obtained from the polytetramethylene terephthalate shows an Izod impact strength (with notch) of 3.4 kg.cm/cm.
Example 5 The polyester type block copolymer chips prepared in Preparation 1 or 2 and polytetramethylene terephthalate (7 sp/c = 1.13) were charged into a drum tumbler, and the mixture was stirred at room tempexature for 30 minutes.
The resulting mixture was extruded with a biaxial extruder (40 mm~). After cooling with water, the extruded product was cut to give chips. The reducing specific viscosity, tensile strength at break and tensile elongation at break of the resulting chips are shown in Table 3.
The chips obtained above were dried at 100C in vacuum and then were formed into a sheet (thickness: 2 mm) with hot-pressing, and the elastic modulus in tension lZ13687 thereof was measured. The results are shown in Table 3.
Moreover, the chips were molded with an injection molding machine to prepare a test piece for measuring Izod impact strength, and the Izod impact strength was measured in the method as described hereinbefore. The results are also shown in Table 3.
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.. . ._. _ . _ 12~ 7 Example 6 The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate (~
sp/c = 1.13) (5 kg), phenyl glycidyl ether (200 g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was extruded with a biaxial extruder (40 mm~)at 230C. After cooling with water, the extruded product was cut to give chips. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example 7 The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate (~sp/c = 1.13) (5 kg), phenyl glycidyl ether (100 g), diethyleneglycol diglycidyl ether (70 g) and triphenylphos-phine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example B
The polyester type block copolymer chips prepared in Preparation 1 (5 kg), polytetramethylene terephthalate ( ~sp/c = 1.13) (5 kg), diethyleneglycol diglycidyl ether (140 't'~
g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, tensile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Example 9 The polyester type block copolymer chips prepared in Preparation 1 (8 kg), polytetramethylene terephthalate (~
sp/c = 1.13) (2 kg), phenyl glycidyl ether (100 g), diethyleneglycol diglycidyl ether (70 g) and triphenylphosphine (10 g) were charged into a drum tumbler, and the mixture was treated in the same manner as described in Example 6. The reducing specific viscosity, tensile strength at break, t~nsile elongation at break, elastic modulus at tension and Izod impact strength of the resulting chips are shown in Table 4.
Table 4 . ~ ..
Ex. No ~sp/c Tensile Tensile Elastic Izod strength elongation modulus impact at bre~k at break at ten~ion strength , (kg/cm ) (%) (kg/cm )(kg cm/cm) 6 1.161 375 425 4670 8.8 7 1.314 467 415 4130 13.4
8 1.352 475 407 4000 16.7
9 1.458 405 520 1980 58.4 In order to compare the properties of the products of Examples 7 to 9 with the products to which no epoxy 12~3tj~37 compound was added, the properties of the pxoduct of Example 2 and also the products which were prepared in the same manner as described in Example 2 except that a conventional stabilizer: Irganox 1010~ (a phenolic stabilizer, manufactured by Ciba-Geigy) (30 g) or Naugard~ (an amine stabilizer, manufactured by Uniroyal Co.) (30 g) were added, were measured likewise. As a result, these latter products were inferior to the former products of Exampl~s 7 to 9 particularly in Izod impact strength.
Example 10 The chips prepared in Preparation 1, Examples 6, 7,and 8 were dried at 100C in vacuum and then were formed into a sheet (thickness: 2mm) with hot-pressing.
Dumbbell-shape test pieces were prepared from the sheet.
The test pieces were kept in a gear oven at 140C for 12 days and thereafter subjected to heat aging test. The results are shown in Table 5. In the table, the retention of strength means the percent (~) of the tensile strength at break of the test piece after subjected to the heat aging test to that before the heat aging test. The retention of elongation is calculated likewise.
1~2:13~87 Table 5 Example No.Retention of Retention of strength (%) Elongation (%) . .. _ .. _ _ Preparn. 1 55 41 Example 6 78 95 ., 7 93 100 " 8 100 100 96 100 ~
For comparison , the products obtained in Example 2 and also using a conventional stabilizer without incorporating an epoxy compound like in the above Table 4 were compared with the products of Examples 6 to 9 as to the heat aging test. As a result, the products containing no epoxy compound were inferior to the products of Examples 6 to 9 in the retention of elongation~
Example 11 The same Dumbbell-shaped test pieces as prepared in Example 10 were kept in hot water of 100C for 5 days, and thereafter, the water resistance of the test pieces was measured, wherein the tensile strength at break and tensile elongation at break of the test pieces were measured before and after the hot water treatment and compared likewise.
The results are shown in Table 6.
Table 6 Example No. Retention of Retention of strength t%) Elongation (~) .
Preparn. 1 Broken (0~ Broken (O) Example 6 54 67 ,~ 7 74 ~ 8S
S " 8 86 1 90.4 " 9 71 1 83 For comparison , the products obtained in Example 2 and also using a conventional stabilizer without incorporating an epoxy compound like in the above Table 4 were compared with the products of Examples 6 to 9 as to the water resistance. As a result, the products containing no epoxy compound were inferior to the products of Examples 6 to 9 in both of the retention of strength and the retention of elongation.
,..;
Example 10 The chips prepared in Preparation 1, Examples 6, 7,and 8 were dried at 100C in vacuum and then were formed into a sheet (thickness: 2mm) with hot-pressing.
Dumbbell-shape test pieces were prepared from the sheet.
The test pieces were kept in a gear oven at 140C for 12 days and thereafter subjected to heat aging test. The results are shown in Table 5. In the table, the retention of strength means the percent (~) of the tensile strength at break of the test piece after subjected to the heat aging test to that before the heat aging test. The retention of elongation is calculated likewise.
1~2:13~87 Table 5 Example No.Retention of Retention of strength (%) Elongation (%) . .. _ .. _ _ Preparn. 1 55 41 Example 6 78 95 ., 7 93 100 " 8 100 100 96 100 ~
For comparison , the products obtained in Example 2 and also using a conventional stabilizer without incorporating an epoxy compound like in the above Table 4 were compared with the products of Examples 6 to 9 as to the heat aging test. As a result, the products containing no epoxy compound were inferior to the products of Examples 6 to 9 in the retention of elongation~
Example 11 The same Dumbbell-shaped test pieces as prepared in Example 10 were kept in hot water of 100C for 5 days, and thereafter, the water resistance of the test pieces was measured, wherein the tensile strength at break and tensile elongation at break of the test pieces were measured before and after the hot water treatment and compared likewise.
The results are shown in Table 6.
Table 6 Example No. Retention of Retention of strength t%) Elongation (~) .
Preparn. 1 Broken (0~ Broken (O) Example 6 54 67 ,~ 7 74 ~ 8S
S " 8 86 1 90.4 " 9 71 1 83 For comparison , the products obtained in Example 2 and also using a conventional stabilizer without incorporating an epoxy compound like in the above Table 4 were compared with the products of Examples 6 to 9 as to the water resistance. As a result, the products containing no epoxy compound were inferior to the products of Examples 6 to 9 in both of the retention of strength and the retention of elongation.
,..;
Claims (5)
1. A polyester block copolymer composition which comprises 2 to 95 parts by weight of a polyester block copolymer obtained from a crystalline aromatic polyester and a lactone, and 98 to 5 parts by weight of a poly-tetramethylene terephthalate, and wherein a mono- or more functional epoxy compound is incorporated therein in an amount of 0.2 to 10 % by weight based on the total weight of the composition.
2. A composition according to claim 1, wherein the amounts of the polyester block copolymer and the polytetra-methylene terephthalate are 25 to 95 parts by weight and 75 to 5 parts by weight, respectively.
3. A composition according to claim 1, wherein the amounts of the polyester block copolymer and the poly-tetramethylene terephthalate are 2 to 24 parts by weight and 98 to 76 parts by weight, respectively.
4. A composition according to claim 1, wherein said mono- or more functional epoxy compound comprises a mono-functional epoxy compound and a di- or more functional epoxy compound incorporated in an amount of 0.1 to 5 % by weight and 0.1 to 9.9 % by weight, respectively, based on the total weight of the composition.
5. A composition according to claim 4, wherein the mono-functional epoxy compound is phenyl glycidyl ether and the di-functional epoxy compound is diethylene diglycidyl ether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP90201/1982 | 1982-05-26 | ||
| JP57090201A JPS58206662A (en) | 1982-05-26 | 1982-05-26 | Polyester block copolymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213687A true CA1213687A (en) | 1986-11-04 |
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ID=13991869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428812A Expired CA1213687A (en) | 1982-05-26 | 1983-05-25 | Polyester block copolymer composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4584353A (en) |
| EP (1) | EP0095189B1 (en) |
| JP (1) | JPS58206662A (en) |
| CA (1) | CA1213687A (en) |
| DE (1) | DE3370014D1 (en) |
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| US4569973A (en) * | 1984-08-24 | 1986-02-11 | General Electric Company | Copolyetheresters from caprolactone |
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| US4839132A (en) * | 1987-02-25 | 1989-06-13 | E. I. Du Pont De Nemours And Company | Process for the preparation of large diameter oriented monofilaments |
| JP2623316B2 (en) * | 1987-10-20 | 1997-06-25 | 東洋紡績株式会社 | Composite damping material and viscoelastic resin composition for damping material |
| IT1245600B (en) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | BLOCK COPOLYESTER RESINS |
| IT1258965B (en) * | 1992-06-10 | 1996-03-11 | PROCEDURE FOR THE PRODUCTION OF POLYESTER RESINS FOR FIBERS | |
| US5356715A (en) * | 1992-07-31 | 1994-10-18 | Morton International, Inc. | Vibration damping resins and vibration damping composites |
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| US5646077A (en) * | 1993-01-07 | 1997-07-08 | Unitika Ltd | Binder fiber and nonwoven fabrics using the fiber |
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| DE4429524C2 (en) * | 1994-08-19 | 1997-12-18 | Inventa Ag | Process for the preparation of linear copolyesters containing omega-hydroxycarboxylic acid units |
| US5869582A (en) * | 1997-01-22 | 1999-02-09 | Alliedsignal Inc. | Diblock polyester copolymer and process for making |
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| TW585880B (en) * | 1999-08-05 | 2004-05-01 | Daicel Chem | Process for producing polyester block copolymer |
| JP3618679B2 (en) * | 2001-04-03 | 2005-02-09 | ダイセル化学工業株式会社 | Polyester block copolymer composition |
| US6949112B1 (en) | 2001-07-26 | 2005-09-27 | Advanced Cardiovascular Systems, Inc. | Medical device formed of polyester copolymer |
| EP1302713A1 (en) * | 2001-10-12 | 2003-04-16 | Dsm N.V. | Thermoplastic cable tie |
| US7420020B2 (en) * | 2004-05-14 | 2008-09-02 | Fuji Xerox Co., Ltd. | Resin particles and producing method thereof, toner for developing electrostatic latent image and producing method thereof, electrostatic latent image developer as well as image forming method |
| WO2005121244A1 (en) * | 2004-06-09 | 2005-12-22 | Lg Cable Ltd. | Polyester resin composition and the cable made of thereit |
| FR3063899B1 (en) | 2017-03-17 | 2019-04-19 | Capsum | COMPOSITIONS COMPRISING A FATTY PHASE AND AQUEOUS PHASE IN THE FORM OF SOLID SPHERES |
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| DE1929149A1 (en) * | 1969-06-09 | 1970-12-23 | Hoechst Ag | Process for the end group modification of polyesters |
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| US4011285A (en) * | 1976-05-14 | 1977-03-08 | Eastman Kodak Company | Molding composition comprising a blend of poly(tetramethylene terephthalate), a polyetherester and a radial teleblock copolymer |
| US4144285A (en) * | 1977-06-06 | 1979-03-13 | Inventa Ag Fur Forschung Und Patent-Verwertung, Zurich | Process for producing hydrolysis-stable shaped structures of polyester |
| US4115350A (en) * | 1977-07-27 | 1978-09-19 | Allied Chemical Corporation | Production of thermally stabilized polyester |
| US4222928A (en) * | 1977-11-09 | 1980-09-16 | Teijin Limited | Polyester composition |
| JPS54139685A (en) * | 1978-04-21 | 1979-10-30 | Toray Industries | Polyester elastomer moldings |
| DE2834032A1 (en) * | 1978-08-03 | 1980-02-28 | Basf Ag | STABILIZED POLYALKYLENE TEREPHTHALATE MOLDING COMPOUNDS |
| JPS5592758A (en) * | 1978-11-06 | 1980-07-14 | Toray Ind Inc | Resin composition |
| GB2039510B (en) * | 1979-01-15 | 1983-04-13 | Gen Electric | Polyester compositions |
| DE3276178D1 (en) * | 1981-01-30 | 1987-06-04 | Teijin Ltd | Polyester resin composition |
| JPS57179239A (en) * | 1981-04-27 | 1982-11-04 | Toyobo Co Ltd | Polyester composition |
| US4374960A (en) * | 1981-09-16 | 1983-02-22 | Allied Corporation | Production of polyester fibers of improved stability |
-
1982
- 1982-05-26 JP JP57090201A patent/JPS58206662A/en active Pending
-
1983
- 1983-05-25 CA CA000428812A patent/CA1213687A/en not_active Expired
- 1983-05-25 EP EP83105142A patent/EP0095189B1/en not_active Expired
- 1983-05-25 DE DE8383105142T patent/DE3370014D1/en not_active Expired
-
1984
- 1984-10-15 US US06/660,618 patent/US4584353A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0095189A2 (en) | 1983-11-30 |
| US4584353A (en) | 1986-04-22 |
| EP0095189A3 (en) | 1984-09-26 |
| JPS58206662A (en) | 1983-12-01 |
| EP0095189B1 (en) | 1987-03-04 |
| DE3370014D1 (en) | 1987-04-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |